Compounded perfumery compositions contain a number of ingredients which may be of natural or synthetic origin. The ingredients are blended by the perfumer to create the desired odor effect. Such essential oils which contain high percentages of hydrocarbon constituents such as patchouli oil (an essential oil derived from Pogostemon Patchouli) have, for example, warm aromatic spicy odors. When the perfumer wishes to include this type of note for example in a perfumery composition of an oriental type, he will use patchouli oil. However, such natural oils as oil of patchouli are expensive essential oils and are of limited availability. Even more extreme examples are natural sandalwood oil and natural vetiver oil. Although, attempts have been made to simulate the odor of patchouli oil, sandalwood oil, and vetiver oil by use of blends of synthetic perfumery chemicals, the creation of such oils having identical aromas with reference to the natural oils has not been achieved.
In U.S. Pat. No. 3,673,120 issued on June 27, 1972, 8-camphene carbinol was indicated to be useful as a perfumery extender for patchouli oil in perfumery compositions when present in a concentration of from 1 to 200 parts by weight per 100 parts by weight of the patchouli oil. However, 8-camphene carbinol has the disadvantage of significantly decreasing the aroma strength of the patchouli oil and is not versatile for use with oils other than patchouli oil, for example, vetiver oil and sandalwood oil in the genus of natural oils, and synthetic oils, for example, geranonitrile and cinnamonitrile.
In U.S. Pat. No. 2,422,145 issued on June 10, 1947, water-soluble hydroxy polyoxyethylene ethers of partial higher fatty acid esters of low molecular weight polyhydroxylic compounds were found to form clear extended solutions with essential oils which could be used as such or which could be diluted with water to form stable dispersions or solutions of essential oils. Specifically disclosed are compositions containing clear, stable solutions of a quantity of an essential oil and at least an equal quantity of such ethers as mannitan monopalmitate hydroxy polyoxyethylene ether with about 20 oxyethylene units per mole with such solution being capable, upon dilution with water, of forming a clear, stable aqueous dispersion of essential oil and hydroxy polyoxyethylene ether. U.S. Pat. No. 2,422,145, however, does not disclose the formation of solutions of essential oil in organic solvents which are immiscible with water. Furthermore, the ethers of U.S. Pat. No. 2,422,145 significantly reduce the strength of the perfumery material when used in conjunction with same.
Cyclohexane dicarboxylic acid diesters having the structure: ##STR1## where R.sub.1 and R.sub.2 are less than 13 carbon aliphatic or alicyclic hydrocarbon moieties are disclosed to be useful "perfume harmonizing agents" in Japanese Published Application at J 52136927 issued on Nov. 15, 1977 to Asahi Denka Kogyo. However, such materials as these cyclohexane dicarboxylic acid diesters detract from the strength of the perfume material with which it is used.
Processes for preparing alpha methyl styrene dimers and methyl homologues thereof are broadly disclosed in the prior art, for example:
French Pat. No. 1,317,412 assigned to Socony Mobil Oil Company dated Feb. 8, 1963; PA1 U.s. pat. No. 3,161,692 issued on Dec. 15, 1964 assigned to Socony Mobil Oil Company; PA1 U.s.s.r. pat. No. 191,511 issued on Jan. 26, 1967; PA1 U.s. pat. No. 3,523,981 assigned to Olin Corporation, issued on Aug. 11, 1970; PA1 Deutsche Offenlegungsschrift 2,101,089 issued on Aug. 10, 1972; PA1 U.s. pat. No. 3,890,402 assigned to Phillips Petroleum Company, issued on June 17, 1975; PA1 Petropoulos and Fisher, J.Am.Chem.Soc. 80, 1938-41 (1958); and PA1 U.s. pat. No. 4,081,489 issued on Mar. 28, 1978 PA1 "The process to manufacture oligomers of camphene by the polymerization of camphene at less than 130.degree. C. and under atmospheric or reduced pressure with the catalysts of ion exchange resin of strong acid type." PA1 "By this invention, the produced oligomers are removed from the reaction system, therefore eliminating the chances of side reactions such as isomerization, hydrolysis, dehydration and oxidation. The products can be obtained in high yield without tetramer or higher oligomers, and are colorless and odorless which are suitable for use in fragrances, cosmetics and food additives."
U.S. Pat. No. 4,081,489 discloses an improved process for the production of compounds having the formula ##STR2## wherein R is independently hydrogen or methyl by contacting a compound of Formula I: ##STR3## where mixture of compounds of Formula I, wherein R is hydrogen or methyl, with a sulfuric acid catalyst at a temperature of 100.degree. to 225.degree. C. which comprises employing a catalyst consisting essentially of about 0.05 up to about 3 weight percent based on the weight of the compound or mixture of compounds of Formula I, of 90 to 98% concentrated sulfuric acid.
Nothing in the prior art teaches the use of alpha methyl styrene dimers, methyl homologues thereof or hydrogenated derivatives thereof as perfume diluents or as perfume extenders. Furthermore, nothing in the prior art teaches the use of hydrogenated derivatives of such alpha methyl styrene dimers or methyl homologues thereof.
In U.S. Pat. No. 3,415,893 issued on Dec. 10, 1968, synthetic pine oil, a material well known to be useful in the perfumery arts was indicated to be synthesized in such a manner that alpha pinene and aqueous sulfuric acid containing emulsifier were agitated under controlled temperature conditions until the content of terpene alcohols reached a maximum. The oil and aqueous phases, in U.S. Pat. No. 3,415,893, are then separated and the oil phase is washed with water containing basic materials to neutralize any residual acid. The oil phase is then distilled to separate the pine oil product from "unreacted alpha pinene and other terpenes, if present as well as from the by-products of the reaction". It is indicated that the by-products are primarily monocyclic hydrocarbons containing some cineols, cyclic ethers and other undesirable products of the reaction and that the by-product portion is a useful solvent. Nothing in U.S. Pat. No. 3,145,893 discloses the usefulness of the diterpene--alpha methyl styrene dimer mixtures of our invention and the advantages thereof as extenders in perfumery.
Diterpenes and hydrogenated diterpenes resulting from the action of various acids on monoterpenes have been studied by various investigators since the discovery over a century ago of dipinene by Deville, Ann. Chim. Phys. [2] 75, 66 (1840) and Ann. Chim. 37, 192 (1840) who obtained dipinene from terpentine oil and sulfuric acid. These experiments of Deville were reviewed as was the literature of synthetic dipinenes in general, by Dulou, Chimie et Industrie, 27 (Special Number) 651 (1932) wherein compounds having the structures of dipinene, indicated to be: ##STR4## were stated to be produced from alpha pinene having the structure: ##STR5## Di-alpha pinene was also produced by Kuwata, J. Faculty Eng. Tokyo Imp. Univ. 18 117-24 (1929) by the action of Japanese acid clay on d-alpha-pinene. In a two-stage reaction, Venable, J. Am. Chem. Soc. 45, 728-34 (1923) treated alpha pinene with Fullers earth causing it first to undergo a molecular rearrangement and then causing a subsequent polymerization to dipinene. Kuwata, in J. Soc. Chem. Ind. Japan 36, Suppl. binding 256-8 (1933) [abstracted in Chem. Abstracts 27:3927] discloses the treatment of camphene in a benzene solution with Japanese acid clay yielding dimer. Camphene dimers are also disclosed to be produced in Japanese Kokai 73 92,355 of Nov. 30, 1973 wherein camphene is passed through a strongly acidic cation exchange resin at one atmosphere and in vacuo at less than or equal to 130.degree. C. to produce camphene dimers and trimers. Japanese Kokai 73 92,355 (Patent Application No. 27686/72) contains the following claim:
In addition, Japanese Kokai 73 92,355 also contains the following relevant disclosure:
The specific properties of the camphene dimers and their utility in the manner described herein as perfumery extenders and diluents are not disclosed in Japanese Kokai 73 92,355, however.
The dimer of limonene is indicated to be prepared from d-limonene by Beilstein V. 509, page 246 (No. 9). The presence of the dimer of limonene is indicated to exist in the essence of Dictamnus Hispanicus in Chem. Abstracts 45:5880 [abstract of "The Essence of Dictamnus Hispanicus", J. Sistare (Inst. `Alonso Barba` Barcelona, Spain) Anales Real Soc. Espan. Fis. Ey. Quim. 47 B, 171-4 (1951)].
In U.S. Pat. No. 2,249,112 issued on July 15, 1941, hydrogenated pinene polymers are indicated to be useful for their "solubility-viscosity characteristics", making them usable as impregnants, adhesive materials, and as a vehicle for metallic paints. They are also indicated to be competable with many mineral oils and can be blended with rubber to produce soft tacky compositions. The hydrogenated pinene polymers indicated to be so produced in U.S. Pat. No. 2,249,112 are produced according to the following reaction scheme: ##STR6## and stated to have the structures: ##STR7##
The hydrogenated terpene polymers of 2,249,112 are not taught to be useful as perfume extenders and are not indicated to have the properties in conjunction with certain perfume essential oils as is disclosed and claimed in the instant application.
Perfume extenders have been broadly used as "adulterants" in the art of perfumery. Thus, for example, in the text entitled "The Art of Perfumery and Method for Obtaining the Odors of Plants" authored by Piesse (Lindsay and Blakiston, Publishers, Philadelphia, 1856) turpentine and spike oil are indicated to be adulterants for lavender oil on page 255. In Poucher "Perfumes and Cosmetics" Van Nostrand Company 1923 terpene residues obtained during the manufacture of concentrated lemon oil are indicated to be adulterants for lemon oil. In Vol. 1 of "The Essential Oils", Guenther, Krieger Publishing Company 1975, Vol. 1 Terpinyl Acetate, and Turpentine Oil (containing d-alpha pinene) are indicated to be used as adulterants. In Vol. 2 of "The Essential Oils" camphorene, a "diterpene" is indicated to be widely applied as fixatives in the sending of soaps. Alpha camphorene has the structure: ##STR8##
U.S. Pat. No. 3,502,769 issued on Mar. 24, 1970, (Fukuhara) discloses a toilet preparation containing a storage-stabilizing amount of a hydrocarbon which may be a mono-cyclic hydrogenated terpene polymer of the formula (C.sub.10 H.sub.19).sub.n and/or a bi-cyclic hydrogenated terpene polymer of the formula (C.sub.10 H.sub.17).sub.n where n is a whole number of from 2 to 4 and a cosmetic base, such as a cold cream or a cleansing cream base. In column 2 of U.S. Pat. No. 3,502,769 at line 15, it is indicated that the hydrogenated terpenes are produced from alicyclic terpene hydrocarbons. It is further indicated that, for example, mono-cyclic terpenes such as menthadienes (e.g., .alpha.-terpinene, .gamma.-terpinene, .alpha.-phellandrene, .beta.-phellandrene, terpinolene, limonene, etc.) and bi-cyclic terpenes such as the camphenes are first polymerized to form hydrocarbon compounds of the formula (C.sub.10 H.sub.16).sub.n, wherein n is a positive whole number from 2 to 4. It is further specified that these polymers are either dimers, trimers or tetramers, and that the resultant polymers are then completely hydrogenated and in the case of the menthadienes, form mono-cyclic polymers of the formula (C.sub.10 H.sub.19).sub.n, wherein n is a whole number of from 2 to 4, and in the case of the bi-cyclic terpenes, it is indicated that there are formed bi-cyclic polymers of the formula (C.sub.10 H.sub.17).sub.n wherein n is a whole number of from 2 ro 4. As an example, when using dipentene as the starting material, the following reaction sequence is stated to take place: ##STR9## Although perfumes are shown to be usable in conjunction with the hydrogenated terpene polymer materials which are further used for the purpose of storage-stabilization, there is no teaching in U.S. Pat. No. 3,502,769 that, in the proportions indicated, the mixtures of (i) such terpene dimerization products as dimerization products of camphene or of .alpha.-pinene or .beta.-pinene and (ii) .alpha.-methyl styrene dimerization products of our invention are useful in the manner described herein as perfumery extenders and diluents.
Plyusnin, et al. in the U.S.S.R. Journal of Applied Chemistry, 29, 1363-1367 also discloses polymerization of individual terpenes (.alpha.-pinene, dipentene and camphene) in the presence of hydrogen fluoride but does not set forth the use of the mixture of our invention in the manner described herein as perfumery extenders and diluents.
Thus, there is no suggestion in the prior art that the mixtures of (i) such terpene dimerization products as dimerization products of camphene or of .alpha.-pinene or .beta.-pinene and (ii) .alpha.-methyl styrene dimers of our invention are useful in the manner described herein as perfumery extenders and diluents.